EP0302308A2 - Verfahren zur Herstellung eines supraleitenden Materials - Google Patents

Verfahren zur Herstellung eines supraleitenden Materials Download PDF

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Publication number
EP0302308A2
EP0302308A2 EP88111693A EP88111693A EP0302308A2 EP 0302308 A2 EP0302308 A2 EP 0302308A2 EP 88111693 A EP88111693 A EP 88111693A EP 88111693 A EP88111693 A EP 88111693A EP 0302308 A2 EP0302308 A2 EP 0302308A2
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EP
European Patent Office
Prior art keywords
mixture
intermediate product
cuo
mixing
oxide
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Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP88111693A
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English (en)
French (fr)
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EP0302308A3 (de
EP0302308B1 (de
Inventor
Yasunobu Ogata
Toshiyuki Kasakoshi
Yusuke Iyori
Kenzi Maruta
Tsutomu Iimura
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Proterial Ltd
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Hitachi Metals Ltd
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Publication date
Priority claimed from JP62195094A external-priority patent/JPS6437466A/ja
Priority claimed from JP62195093A external-priority patent/JPS6437465A/ja
Application filed by Hitachi Metals Ltd filed Critical Hitachi Metals Ltd
Publication of EP0302308A2 publication Critical patent/EP0302308A2/de
Publication of EP0302308A3 publication Critical patent/EP0302308A3/de
Application granted granted Critical
Publication of EP0302308B1 publication Critical patent/EP0302308B1/de
Anticipated expiration legal-status Critical
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    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/45—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on copper oxide or solid solutions thereof with other oxides
    • C04B35/4521—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on copper oxide or solid solutions thereof with other oxides containing bismuth oxide
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/45—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on copper oxide or solid solutions thereof with other oxides
    • C04B35/4504—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on copper oxide or solid solutions thereof with other oxides containing rare earth oxides
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/45—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on copper oxide or solid solutions thereof with other oxides
    • C04B35/4512—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on copper oxide or solid solutions thereof with other oxides containing thallium oxide
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N60/00—Superconducting devices
    • H10N60/01—Manufacture or treatment
    • H10N60/0268—Manufacture or treatment of devices comprising copper oxide
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S505/00—Superconductor technology: apparatus, material, process
    • Y10S505/725—Process of making or treating high tc, above 30 k, superconducting shaped material, article, or device
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S505/00—Superconductor technology: apparatus, material, process
    • Y10S505/775—High tc, above 30 k, superconducting material
    • Y10S505/776—Containing transition metal oxide with rare earth or alkaline earth
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S505/00—Superconductor technology: apparatus, material, process
    • Y10S505/775—High tc, above 30 k, superconducting material
    • Y10S505/776—Containing transition metal oxide with rare earth or alkaline earth
    • Y10S505/777—Lanthanum, e.g. La2CuO4
    • Y10S505/778—Alkaline earth, i.e. Ca, Sr, Ba, Ra
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S505/00—Superconductor technology: apparatus, material, process
    • Y10S505/775—High tc, above 30 k, superconducting material
    • Y10S505/776—Containing transition metal oxide with rare earth or alkaline earth
    • Y10S505/779—Other rare earth, i.e. Sc,Y,Ce,Pr,Nd,Pm,Sm,Eu,Gd,Tb,Dy,Ho,Er,Tm,Yb,Lu and alkaline earth, i.e. Ca,Sr,Ba,Ra
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S505/00—Superconductor technology: apparatus, material, process
    • Y10S505/775—High tc, above 30 k, superconducting material
    • Y10S505/776—Containing transition metal oxide with rare earth or alkaline earth
    • Y10S505/779—Other rare earth, i.e. Sc,Y,Ce,Pr,Nd,Pm,Sm,Eu,Gd,Tb,Dy,Ho,Er,Tm,Yb,Lu and alkaline earth, i.e. Ca,Sr,Ba,Ra
    • Y10S505/78—Yttrium and barium-, e.g. YBa2Cu307
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S505/00—Superconductor technology: apparatus, material, process
    • Y10S505/775—High tc, above 30 k, superconducting material
    • Y10S505/776—Containing transition metal oxide with rare earth or alkaline earth
    • Y10S505/779—Other rare earth, i.e. Sc,Y,Ce,Pr,Nd,Pm,Sm,Eu,Gd,Tb,Dy,Ho,Er,Tm,Yb,Lu and alkaline earth, i.e. Ca,Sr,Ba,Ra
    • Y10S505/78—Yttrium and barium-, e.g. YBa2Cu307
    • Y10S505/781—Noble metal, i.e. Ag, Au, Os, Ir, Pt, Ru, Rh, Pd or chromium, manganese, iron, cobalt or nickel

Definitions

  • This invention relates to a method for producing superconducting materials of oxide type ceramics and, more particularly, to a method for producing the super­conducting materials which is improved so that raw materials can readily be uniformly mixed, localization of composition can be prevented and thus uniform composi­tions can be obtained.
  • the ceramic superconducting materials are generally synthesized by application of powder metallurgy. That is, for example, Y-Ba-Cu-O ceramics (YBCO) are obtained by mixing powders of raw materials BaCO3, Y2O3 and CuO, calcining the mixture at 900°C to carry out a solid phase reaction, then grinding the mixture and press molding the resulting powder into pellets and then sintering the molded product in an oxygen atmosphere.
  • YBa-Cu-O ceramics YBCO
  • YBCO Y-Ba-Cu-O ceramics
  • uniformly mixing the above three raw material powders is relatively difficult and besides, mixing requires a long time due to the difference in specific gravity, shape and particle size.
  • the object of this invention is to provide a method for producing superconducting materials having a uniform texture and a high sintered density and current density with no problems mentioned above.
  • this invention provides a method for production of oxide type superconducting materials of layered perovskite structure containing Cu (copper) and O (oxygen) as basic constituting elements wherein a raw material CuO and the other raw material, i.e., a carbonate or oxide or mixture thereof are allowed to react previously to obtain at least one intermediate product containing Cu and O and then these intermediate products (in case two or more intermediate products are produced) or the intermediate product and other raw material (in case only one intermediate product is produced) are subjected to final reaction to obtain an oxide of a layered perovskite structure having the desired final composition and texture.
  • a raw material CuO and the other raw material i.e., a carbonate or oxide or mixture thereof are allowed to react previously to obtain at least one intermediate product containing Cu and O and then these intermediate products (in case two or more intermediate products are produced) or the intermediate product and other raw material (in case only one intermediate product is produced) are subjected to final reaction to obtain an oxide of a layered perovskite structure
  • A is at least one selected from Sc, Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy( Ho, Er, Tm, Yb and Lu or a mixture of two or more of them
  • B is at least one selected from Ba, Sr and Ca or a mixture of two or more of them
  • C is Cu or a Cu based mixture of Cu with at least one selected from Ti, V, Cr,Mn, Fe, Co, Ni and Zn or with two or more of them, and ⁇ is more than zero but less than 0.5; raw materials comprising compounds containing A and C, respectively are mixed and then the mixture is calcined to produce an oxide contain­ing A and C and separately raw materials comprising compounds containing B and C, respectively are mixed and then the mixture is calcined to obtain an oxide containing B and C and the resulting two oxides are mixed and sintered in an oxygen atmosphere.
  • Bi2O3 and CuO are mixed and the mixture is calcined to produce a first intermediate product containing Bi and Cu of the above two oxides.
  • SrCO3, CaCO3 and CuO are mixed and the mixture is calcined to produce a second intermediate product containing Sr, Ca and Cu.
  • the first intermediate product and the second intermediate product are mixed and the mixture is sintered in an oxygen atmosphere to obtain Bi-Sr-Ca-Cu-O type oxide of layered perovskite structure.
  • the pellets were sintered at 1000°C for 4 hours in an oxygen atmosphere to produce a superconducting material of a triple-layer perovskite structure deficient in oxygen.
  • the average particle size of powders in the above steps is preferably 0.2 - 0.5 ⁇ m.
  • the characteristics of the resulting superconducting material were measured to obtain a critical temperature of 91 K and a current density of 5000 A/cm2.
  • Figs. 1 and 2 are photographs which show the crystal structure of the superconducting material obtained in this example and a conventional superconducting material, respectively.
  • black portions are cavities or vacancies which are discontinuous portions in crystal structure.
  • the material of this example of Fig. 1 had very few vacancy portion and had a high sintered density.
  • Fig. 2 which shows a conventional superconducting material indicates a great number of vacancy portions and this means a low sintered density.
  • the sintered density of the former was 95% and that of the latter was 60 - 70%.
  • A is one element selected from Sc, Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu or a mixture of two or more of these elements
  • B is one element selected from Ba, Sr and Ca or a mixture of two or more of these elements
  • C is Cu or a mixture mainly composed of Cu which comprises Cu with one element selected from Ti, V, Cr, Mn, Fe, Co, Ni and Zn or with two or more elements selected from these elements, and ⁇ is more than zero but less than 0.5. It is effective for obtaining a further uniform texture to mix an oxide containing A and C and an oxide containing B and C and then calcine the mixture in the same manner as above.
  • This invention has the effects based on the above-mentioned construction and such an action that superconducting materials having a uniform texture and markedly high sintered density and current density can very easily be produced.
  • Average particle size of the powders in the above steps is preferably 0.2 - 0.5 ⁇ m.
  • the characteristics of the thus obtained superconducting material were measured to obtain a critical temperature of 91 K and a current density of 5000 A/cm2.
  • the material had a sintered density of 95%.
  • A is one element selected from Sc, Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu or a mixture of two or more of these elements
  • B is one element selected from Ba, Sr and Ca or a mixture of two or more of these elements
  • C is Cu or a mixture mainly composed of Cu which comprises Cu with one element selected from Ti, V, Cr, Mn, Fe, Co, Ni and Zn or with two or more elements selected from these elements
  • ⁇ is more than zero but less than 0.5. It is effective for obtaining a further uniform texture to mix an oxide containing A and C in the above compositional formula and an oxide containing B and C and then calcine the mixture in the same manner as above.
  • This invention has the effects based on the above-mentioned construction and such an action that superconducting materials having a uniform texture and markedly high in sintered density and current density can very easily be produced.
  • the average particle size of the powders in the steps above is preferably 0.2 - 0.5 ⁇ m.
  • the characteristics of the thus obtained superconducting material were measured to obtain a critical temperature of 91 K and a current density of 1000 A/cm2.
  • the material had a sintered density of 95%.
  • a target material of 100 mm in diameter and 5 mm in thickness was prepared from the above composition and held on a backing plate and a thin film of YBa2Cu3O 7- ⁇ having a thickness of 5000 ⁇ was formed by a sputtering method comprising irradiation with Ar ion. The characteristics of this thin film were measured to obtain a critical temperature of 90 K and a current density of 2500 A/cm2.
  • A is one element selected from Sc, Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu or a mixture of two or more of these elements
  • B is one element selected from Ba, Sr and Ca or a mixture of two or more of these elements
  • C is Cu or a mixture mainly composed of Cu which comprises Cu with one element selected from Ti, V, Cr, Mn, Fe, Co, Ni and Zn or with two or more elements selected from these elements
  • ⁇ is more than zero but less than 0.5. It is effective for obtaining a further uniform texture to mix an oxide containing A and C in the above-mentioned compositional formula and an oxide containing B and C and then calcine the mixture in the same manner as above.
  • BiCaSrCu2O 7- ⁇ Bi based oxide superconducting material represented by BiCaSrCu2O 7- ⁇
  • this invention is not limited to this type, but can be similarly applied to other Bi based oxide superconducting materials.
  • This invention has been explained with reference to a Bi-Sr-Ca-Cu-O type oxide superconducting material, this invention can also be applied to super­conducting materials of Tl-Ca-Ba-Cu-O (for example, Tl2Ca2Ba2Cu3O 7- ⁇ , Tl2Ca1Ba2Cu2O 7- ⁇ and the like).
  • the product was filled in a pipe of 5 mm in outer diameter, 4 mm in inner diameter and 300 mm in length and was sintered to produce a superconducting material having a triple-layer perovskite structure deficient in oxygen and having the composition of YBa2Cu3O 7- ⁇ .
  • Fig. 3 schematically shows the sintering means in the above example.
  • 1 indicates a silica glass tube having an outer diameter of 180 mm, an inner diameter of 174 mm and a length of 1400 mm which supports pipe 3 of Al2O3 by means of supporting member 2 of SiC.
  • 4 indicates a raw material powder and was filled in pipe 3 as mentioned above and the pipe was closed.
  • 5 indicates a high frequency coil which is provided outside the silica glass tube 1 in such a manner that it can freely move in axial direction.
  • the high frequency coil 5 was formed to have a length of, for example, 20 mm to provide a high temperature zone w of 10 - 30 mm where pipe 3 and raw material powder 4 were heated. Then, the high frequency coil 5 was moved at a speed of 30 mm/Hr from the right end portion of pipe 3 in the direction indicated by arrow and accordingly said high temperature zone also moved gradually to the left. By repeating this operation three times, it was possible to perform solid phase sintering and/or liquid phase sintering due to partial dissolution of raw material powder filled in pipe 3 . In this case, since the high temperature zone gradually moved from the right end of pipe 3 to the left, temperature gradient was imparted to the raw material powder 4 in the pipe 3 and this causes alignment of crystal grains and crystal axis in the axial direction of pipe 3 .
  • raw material powders were calcined, then disintegrated and ground, press molded into pellets of 5 mm in diameter x 2 mm and then sintered at 950°C for 4 hours in an oxygen atmosphere.
  • Crystal grains of YBa2Cu3O 7- ⁇ in conven­tional examples were distributed in the form of amorphous particles or masses and the direction of crystal axis was not alinged at all.
  • it was recognized that the crystal grains of the product of this example were completely aligned in the axial direction of pipe 3 .

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Ceramic Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Oxide Ceramics (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)
EP88111693A 1987-08-04 1988-07-20 Verfahren zur Herstellung eines supraleitenden Materials Expired - Lifetime EP0302308B1 (de)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP195093/87 1987-08-04
JP195094/87 1987-08-04
JP62195094A JPS6437466A (en) 1987-08-04 1987-08-04 Production of superconducting material
JP62195093A JPS6437465A (en) 1987-08-04 1987-08-04 Production of superconducting material

Publications (3)

Publication Number Publication Date
EP0302308A2 true EP0302308A2 (de) 1989-02-08
EP0302308A3 EP0302308A3 (de) 1991-01-09
EP0302308B1 EP0302308B1 (de) 1994-12-07

Family

ID=26508920

Family Applications (1)

Application Number Title Priority Date Filing Date
EP88111693A Expired - Lifetime EP0302308B1 (de) 1987-08-04 1988-07-20 Verfahren zur Herstellung eines supraleitenden Materials

Country Status (4)

Country Link
US (1) US5032570A (de)
EP (1) EP0302308B1 (de)
CN (1) CN1031149A (de)
DE (1) DE3852353T2 (de)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101315845B1 (ko) 2012-10-22 2013-10-08 강원대학교산학협력단 고온 초전도체 Ｌｕ-123의 제조방법

Families Citing this family (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5145834A (en) * 1988-02-12 1992-09-08 University Of Arkansas Processes for making Tl-Ca-Ba-Cu-O, Tl-Sr-Ba-Cu-O and Tl-Sr-Cu-O superconductors by solid state synthesis
DE69029260D1 (de) * 1989-02-16 1997-01-09 Ramon Galvan D Cavazos Supraleitende Zusammensetzungen und Verfahren zu ihrer Herstellung
JPH0696467B2 (ja) * 1990-01-29 1994-11-30 日本碍子株式会社 ＭｇＯ系β”―アルミナ焼結体の製造方法
US5300483A (en) * 1992-01-16 1994-04-05 Sinha Shome N Process for preparing shaped superconductor materials via nonequilibrium precursors
US5354535A (en) * 1993-04-06 1994-10-11 University Of Chicago Synthesis of highly phase pure (Bi, Pb)-Sr-Ca-Cu-O superconductor
WO1995025177A1 (en) 1994-03-15 1995-09-21 Scientific Generics Limited Electrochemical denaturation of double-stranded nucleic acid
US5591698A (en) * 1994-12-29 1997-01-07 University Of Hawaii Low temperature (T lower than 950° C.) preparation of melt texture YBCO superconductors
US6743605B1 (en) 1998-06-24 2004-06-01 Enzo Life Sciences, Inc. Linear amplification of specific nucleic acid sequences
US8445664B2 (en) 1998-06-24 2013-05-21 Enzo Diagnostics, Inc. Kits for amplifying and detecting nucleic acid sequences
EP2562769A4 (de) * 2010-04-21 2014-07-30 Fujikura Ltd Oxidsupraleiter und herstellungsverfahren dafür
CN116409991A (zh) * 2017-06-15 2023-07-11 中岛产业株式会社 黑色混合氧化物材料及其制造方法
CN113470883B (zh) * 2021-06-29 2022-11-11 南京大学 具有高临界参数无毒铜氧化物超导体及其制备方法

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Publication number Priority date Publication date Assignee Title
JPS4923996B1 (de) * 1964-06-10 1974-06-19
GB1405012A (en) * 1972-01-21 1975-09-03 Ici Ltd Method of making composition convertible to a catalyst precursor and catalyst and methanol synthesis using the catalyst
DE2653985A1 (de) * 1976-11-27 1978-06-01 Hoechst Ag Katalysator zur reduktion von kohlenmonoxid mit wasserstoff
US4408067A (en) * 1979-01-26 1983-10-04 Nitto Chemical Industries, Ltd. Process for producing carboxylic acid esters from nitriles
JPS63288944A (ja) * 1987-05-22 1988-11-25 Hitachi Ltd 高温超電導体の作製方法
US4857504A (en) * 1987-08-25 1989-08-15 University Of Arkansas Melt-produced high temperature rare earth barium copper oxide superconductor and processes for making same

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101315845B1 (ko) 2012-10-22 2013-10-08 강원대학교산학협력단 고온 초전도체 Ｌｕ-123의 제조방법

Also Published As

Publication number Publication date
DE3852353D1 (de) 1995-01-19
EP0302308A3 (de) 1991-01-09
DE3852353T2 (de) 1995-06-29
EP0302308B1 (de) 1994-12-07
US5032570A (en) 1991-07-16
CN1031149A (zh) 1989-02-15

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